Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/08—Printing inks based on natural resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
  • C09D191/005—Drying oils
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
  • C09D191/02—Vulcanised oils, e.g. factice
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
  • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
  • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
  • H01L29/47—Schottky barrier electrodes

Definitions

• THIS invention relates to printable compositions for use in electronic and electrical applications in general, and specifically in those applications where semiconducting properties are required.
• Nanoparticles with a characteristic size of a few nanometres up to several hundred nanometres, are a widely studied type of material, in which size effects dominate over properties of the bulk material. In general, depending on the specific material and its application, three different size-related phenomena may change the electronic, optical, thermal and mechanical properties of such nanoparticles:
• organic semiconducting inks comprising semiconducting particles dispersed randomly in a matrix or binder, and inorganic semiconducting inks in which the semiconducting particles form an interconnecting structure, are known.
• the binder or matrix material is often a polymer which is soluble in an easily obtainable solvent, such as acetone, chloroform or toluene.
• an easily obtainable solvent such as acetone, chloroform or toluene.
• Common examples are polystyrene and cellulose acetate butyrate (CAB), which are insulators, and polythiophenes which are conjugated hole conductors, allowing charge transport between isolated particles.
• a method of producing a printable composition comprising mixing a quantity of particulate semiconductor material with a quantity of a binder, wherein the binder is a self-polymerising material comprising a natural oil, or a derivative or synthetic analogue thereof.
• the binder may comprise a natural polymer formed by auto-polymerisation of a precursor consisting of a natural oil, or its derivatives including pure unsaturated fatty acids, mono- and di-glycerides, or methyl and ethyl esters of the corresponding fatty acids.
• the binder may comprise a drying or semi-drying oil, or a mixture thereof.
• the drying oil may contain one or more octadecanoic acids, octadecadienoic acids, and/or octadecatrienoic acids.
• the drying oil is linseed or tung oil.
• the oil may be soy-bean, cottonseed or castor oil, for example.
• the binder may be an octadecadienoic acid or an octadecatrienoic acid, or a mixture thereof.
• the binder may be linolenic acid or linoleic acid.
• the method may include mixing the binder with a solvent, such as ethanol, acetone or lacquer thinners.
• a solvent such as ethanol, acetone or lacquer thinners.
• the composition may be applied to the substrate as a lacquer, comprising the binder and the particles, or may be applied as a varnish, comprising the binder, the particles, and a solvent.
• the volume ratio of the particulate semiconductor material to the binder is greater than 50%, and more preferably greater than 80%.
• the particulate semiconductor material may have a particle size in the range from 5 nanometres to 10 microns, and preferably in the range from 50 to 500 nanometres.
• the size range may be from 100 to 300 nanometres.
• the particulate semiconductor material comprises silicon
• a method of producing an electronic component or conductor comprising preparing a printable composition as defined above, applying the printable composition to a substrate, and allowing the printable composition to cure to define the component or conductor on the substrate.
• the printable composition may be applied in a single application or in multiple layers to define electronic components with desired characteristics.
• the printable composition is allowed to cure under ambient conditions.
• the substrate may be rigid or flexible, and may comprise, for example, metal, glass, plastics, and paper.
• the printable composition may be applied in a layer having a thickness in the range from 0.1 to 500 microns.
• the layer has a thickness in the region of 100 microns.
• the invention extends to a printable composition, and to an electronic component or conductor, produced by the respective method.
• Figure 1(a) is a schematic sectional diagram illustrating dispersed semiconductor particles in a binder layer deposited on a substrate, according to a first embodiment of the invention
• Figure 1(b) is a schematic sectional diagram similar to that of Figure 1 (a) illustrating an interconnecting network of semiconductor particles in a binder layer deposited on a substrate, according to a second embodiment of the invention
• Figure 1(c) is a schematic sectional diagram similar to that of Figures 1 (a) and 1(b) illustrating semiconductor particles concentrated in the lower part of a binder layer deposited on a substrate, according to a third embodiment of the invention
• Figure 1(d) is a schematic sectional diagram similar to that of Figures 1 (a) to (c) illustrating semiconductor particles concentrated in the upper part of a binder layer deposited on a substrate, according to a fourth embodiment of the invention
• Figure 2 is a schematic diagram of a natural oil suitable for use in the method of the invention.
• Figure 3 is a graph illustrating characteristic curves of Schottky diodes manufactured according to the method of the invention, using different binder materials.
• Figure 4 is a graph illustrating the conductance of semiconducting layers, produced from silicon inks using linoleic and linolenic acid as binders, as a function of the applied gate potential in a transistor test structure.
• compositions for use in electronic and electrical applications in general, and specifically in those applications where semiconducting properties are required.
• These compositions which can be used in the production of electronic circuits, components and as composite materials for the production of semiconducting materials and layers, comprise particles with a semiconducting functionality and a self- polymerising binder, preferably of natural origin, which cures through oxidation or hydroxation induced auto-polymerisation.
• any such printable composition generally known as an ink, lacquer, paint, varnish, suspension or the like is referred to as an "ink”.
• Methods of applying the ink including spraying, casting and painting, as well as conventional intaglio, flat or relief printing techniques, are generally referred to as "printing”.
• Dry transfer methods such as xerography and thermal printing may be included if the melting point and viscosity of the binder are such that it is solid under normal conditions.
• the above types of printable composition and methods of application thereof are given by way of example and other examples may occur to those skilled in the art.
• the binder or matrix material is a polymer such as polystyrene or cellulose acetate butyrate (CAB), which is soluble in an easily obtainable solvent, such as acetone, chloroform or toluene.
• CAB cellulose acetate butyrate
• binder-particle mixtures are well known in the traditional crafts as inks, lacquers and varnishes, in which inorganic particles serve as a pigment.
• the pigment is mixed with a natural drying oil which polymerises through auto-oxidation, although more recently synthetic monomers have been applied, which may also polymerise through hydroxation.
• the binder is thinned with a suitable organic solvent, such as ethanol or methanol, or mixture of solvents, such as commercial lacquer thinners.
• a suitable organic solvent such as ethanol or methanol
• solvents such as commercial lacquer thinners.
• the addition of a thinner serves the dual purpose of adjusting the rheology of the liquid and preventing premature hardening, thus prolonging storage times.
• the natural origin and limited processing of these binder materials leads them to be considered as ecologically friendly renewable resources.
• the semiconductor particles need to be uniformly dispersed in the binder material as shown schematically in Figure 1(a). To achieve this the interfacial tension between the two materials needs to be low, to allow complete wetting of the particles.
• the viscosity of the ink should be kept high during deposition and curing to prevent sedimentation or flocculation of the particles.
• the ink should contain a high volume fraction of the semiconducting particles relative to the binder material, so that the final material contains an interconnecting network of particles, as shown schematically in Figure 1(b), which may have a regular or fractal geometry.
• the ink may, however, for application or storage, be diluted with any quantity of solvent or thinner, including water or a non- reactive organic liquid.
• the interfacial tension between the particles and the binder is therefore of little significance, although a higher value may help prevent complete wetting of the interstices between the particles, thus promoting a better conducting path between adjacent particles.
• separation through settling or flocculation as shown schematically in Figures 1(c) and 1(d), respectively, may be beneficial in the production of bilayer systems and components consisting of semiconducting and insulating layers, such as MIS-FETs and capacitors.
• the printed layers or components will typically have a thickness in the range from 0.1 to 500 microns.
• the binder material should be a natural polymer formed by auto- polymerisation of a precursor consisting of a natural oil, or its derivatives including pure unsaturated fatty acids, mono- and di-glycerides, as well as methyl and ethyl esters of the corresponding fatty acids.
• Natural oils are generally a complex mixture of triglycerides, with three randomly selected fatty acids attached to a glycerol (propan-1-2-3-triol) backbone, as shown in Figure 2. Their composition, therefore, depends strongly on both the plant species and its cultivation, but through blending a consistent quality with regard to curing properties and fatty acid fractions is usually obtained.
• the volume ratio of the particulate semiconductor material to the binder should greater than 50%, and more preferably greater than 80%. In two of the examples below, a volume ratio of the order of 90% was used.
• the particulate semiconductor material may have a particle size in the range from 5 nanometres to 10 microns, and is preferably nanoparticulate, with a size in the range from 50 to 500 nanometres.
• drying oils responsible for polymerisation are the octadecanoic acids, characterised by one double bond, the octadecadienoic acids, with two double bonds, and the octadecatrienoic acids (three double bonds).
• Other unsaturated fatty acids also contribute to the polymerisation, with the non-polymerised saturated fatty acids acting as plasticisers.
• octadecatrienoic acids are all conjugated trans-fatty acids, with alternating double and single bonds, and polymerise the most effectively.
• the exception is linolenic acid (9cis-12cis-15cis- octadecatrienoic acid), which is a non-conjugated cis-fatty acid and is the major component of linseed oil.
• linseed oil the main drying oil used in coatings is tung oil, also known as china wood oil, whose main polymerising component is eleostearic acid (9cis-11trans-13trans- octadecatrienoic acid). Both of these oils have the advantage of being inexpensive and readily available compared to both synthetic binders and other natural oils.
• Table 1 examples of plant oils with significant concentrations of octadecatrienoic acids suitable as self-polymerising binders for semiconductor composite materials.
• semidrying oils such as soy-bean, cottonseed and castor oil
• soy-bean, cottonseed and castor oil may be used to supplement, or even replace the drying oils.
• the major active components of these oils are linoleic (9cis-12cis-octadecadienoic) acid and ricolenic (12-hydroxy-9-octadecanoic) acid.
• Oil-based semiconducting inks are particularly well suited to offset lithography and other flat printing processes, because of their intrinsic hydrophobicity.
• the oils are soluble in most easily available non-aggressive solvents, such as ethanol or acetone, allowing simple and safe modification of their viscosity and cleaning.
• drying agents are metallic salts of organic acids, and contain ionic groups which can affect the doping level of semiconducting particles, and may also lead to electrical conductivity in otherwise insulating layers.
• the pure fatty acids are polar molecules which are water soluble, making them suitable for water-based compositions for relief and intaglio printing processes. Without the other components found in the oil, they will form a denser, less flexible polymer, and will cure much more rapidly.
• dienoic acids such as linoleic (9cis-12cis-octadecadienoic) acid, which is the most common unsaturated fatty acid found in almost all plants, will polymerise to form suitable binders.
• the pure acids are non- aggressive and soluble in mild solvents like alcohols and ethers which do not attack common materials (e.g. synthetic and natural rubbers, plastics) used in printing processes.
• Analogues of the oils which can also be used as self-polymerising binders for semiconducting inks, include the mono- and di-glycerides and the methyl and ethyl esters of the unsaturated fatty acids. These are effectively intermediate forms, in which systematic removal of saturated acids, while keeping the molecules non-polar, allows the rapid polymerisation associated with pure acids and the hydrophobic properties of the oils.
• Substrates on which the printable compositions can be deposited may be rigid or flexible, according to requirements.
• Possible rigid substrates include glass, metals and stiff or rigid plastics.
• Flexible substrates can be, for example, flexible plastics, thin metallic layers or paper.
• the first example concerns the production of semiconducting inks composed of nanoparticulate silicon with raw linseed oil as a self- polymerising binder.
• the silicon nanoparticles were produced by mechanical attrition, for 3 hours in an orbital pulveriser, of bulk silicon. Both single crystalline wafers, boron-doped P type and antimony-doped N type, and metallurgical grade silicon were used. Typical particle sizes were between 100 and 300 nm.
• Inks were produced by first diluting the oil with ethanol as a carrier solvent, and then dispersing the nanopowders at a high volume ratio, in excess of 90%, relative to the oil. Layers, typically 100 microns thick, were then printed onto paper substrates. Electrical connections for Hall effect measurements were then applied using printable silver conductor screen printing ink (Du Pont 5000). The majority carrier mobilities and concentrations, as determined by the Hall effect, are given in Table 2 below.
• Table 2 Semiconducting characteristics of inks produced from various silicon nanoparticles, using raw linseed oil as a self-polymerising binder and ethanol as a solvent
• the second example concerns the production of semiconducting inks made with different natural oils as self-polymerising binders and metallurgical grade silicon nanoparticles.
• the silicon nanoparticles were produced by mechanical attrition of the bulk material for 180 minutes in an orbital pulveriser.
• Inks were produced by mixing 20 microlitres of oil with 0.5 g silicon powder, and thinning with 50 microlitres of commercial laquer thinners, to achieve complete wetting. The mixture was then agitated for 40 minutes in an ultrasonic bath to achieve a homogeneous dispersion of the silicon powder.
• the following oils were compared: linseed oil; castor oil; soy bean oil; calendula oil; and a blend of calendula with non-drying oils.
• a third example concerns the use of the fatty acids, linolenic (9cis-12cis-15- cis-octadecatrienoic) acid and linoleic (9cis-12cis- octadecadienoic) acid, in semiconducting inks.
• fatty acids linolenic (9cis-12cis-15- cis-octadecatrienoic) acid and linoleic (9cis-12cis- octadecadienoic) acid
• a silver gate contact was first printed, using Du Pont 5000 silver conductor screen printing ink, onto a 350 gsm Euro Art glossy paper substrate by tampon printing. The size of this electrode was 1 mm by 3 mm. Over this, an insulating layer was tampon printed, using Du Pont 8153 insulator. Finally, the source and drain electrodes, also Du Pont 5000 silver conductor, were overprinted using the same method. The gate length and width in the final structure were 120 ⁇ m and 1 mm respectively.
• the structures were dried in an oven at 120 0 C for 30 minutes after printing the insulator, and after printing the final silver contacts.
• the electrical characteristics of the device structure, without application of the semiconducting layer, were also determined.
• inks 2503 metallurgical grade silicon, from Silicon Smelters (Pty) Ltd, Polokwane, South Africa, milled for three hours in an orbital pulveriser; and intrinsic silicon nanopowder, from MTI Crystal Corp, which had a specified particle size less than 50 nm.
• inks were produced with a volume fraction of silicon at the lower limit of 50%, comprising 0.4 g silicon powder added to a solution of 200 microlitres of the respective binder in an appropriate volume of commercial lacquer thinners.
• the quantity of solvent was kept the same for each type of powder, namely 1.2 ml for the metallurgical grade silicon and 4.8 ml for the smaller intrinsic nanoparticles.
• the mixtures were sonicated in an ultrasonic bath for two hours. Approximately five microlitres of each ink was either hand printed, or drop cast, onto the gate of a different pre- prepared structure, and allowed to dry overnight. The printed layers showed a high integrity, forming a continuous film without being powdery, whereas drop cast layers developed surface cracks during drying. All layers showed good adhesion to the substrate.
• the characteristic curves of each structure were determined using a Keithley 4200 semiconductor characterisation system, for drain-source potentials up to 20V, and gate potentials of 0, ⁇ 5 V, ⁇ 10 V, and ⁇ 15 V.
• the geometry and dimensions of the test structure were such that saturation of the drain-source current could not be attained, and only a weak field effect was observed. All devices, therefore, exhibited a linear response, with an offset for applied gate potential indicating a finite gate-drain resistance.
• the source-drain conductance for each device, after correction for the gate- drain current, is shown as a function of the applied gate potential in Figure 4.
• the conductance is higher for the printed layers compared to the bare device structure, indicating that there is electrical connectivity between the particles, even with the high binder fractions used.
• the conductance is dependent on the applied gate voltage, confirming that the printed layers are indeed semiconducting.

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• Condensed Matter Physics & Semiconductors (AREA)
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• Physics & Mathematics (AREA)
• Computer Hardware Design (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Conductive Materials (AREA)
• Thin Film Transistor (AREA)
• Electrodes Of Semiconductors (AREA)
• Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

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• 2006
  • 2006-12-18 ES ES06842244.3T patent/ES2609413T3/es active Active
  • 2006-12-18 EP EP06842244.3A patent/EP1971651B1/en not_active Not-in-force
  • 2006-12-18 KR KR1020087018039A patent/KR101407252B1/ko active IP Right Grant
  • 2006-12-18 WO PCT/IB2006/003666 patent/WO2007072162A1/en active Application Filing
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